Semiconductor device and forming method thereof

ABSTRACT

A device includes a substrate, a first zirconium-containing oxide layer, a first metal oxide layer and a top electrode. The first zirconium-containing oxide layer is over a substrate and having ferroelectricity or antiferroelectricity. The first metal oxide layer is in contact with the first zirconium-containing oxide layer. The first metal oxide layer has a thickness less than a thickness of the first zirconium-containing oxide layer. The top electrode is over the first zirconium-containing oxide layer.

PRIORITY CLAIM AND CROSS-REFERENCE

This application claims priority to U.S. Provisional Patent Application Ser. No. 62/712,196, filed Jul. 30, 2018, which is herein incorporated by reference in its entirety.

BACKGROUND

The subthreshold swing is a feature of a transistor's current-voltage characteristic. In the subthreshold region the drain current behavior is similar to the exponentially increasing current of a forward biased diode. A plot of logarithmic drain current versus gate voltage with drain, source, and bulk voltages fixed will exhibit approximately logarithmic linear behavior in this metal-oxide-semiconductor field-effect transistor (MOSFET) operating region. To improve the subthreshold properties, a negative capacitance field effect transistor (NC-FET) using a ferroelectric material has been proposed.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the following detailed description when read with the accompanying figures. It is noted that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion.

FIGS. 1A and 1B are diagrams showing energy versus polarization for ferroelectricity and antiferroelectricity, respectively.

FIG. 2A is a diagram showing transient currents integrated during an electric field with a triangular-shaped wave in which Ec is coercive field.

FIG. 2B is a diagram showing an ac excitation signal, which is expressed as E(t), a function of time.

FIG. 2C is a diagram showing an exemplary polarization-electric field (P-E) hysteresis loop of a ferroelectric material.

FIG. 3A is a diagram showing current density versus electric field for antiferroelectricity.

FIG. 3B is a diagram showing polarization versus electric field for antiferroelectricity.

FIGS. 4A and 4D are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 4B and 4C are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIG. 4A.

FIG. 4E is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure in FIG. 4D.

FIGS. 5A-5C illustrate fabrication of the semiconductor structure of FIG. 4D in accordance with some embodiments of the present disclosure.

FIGS. 6A and 6C are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 6B and 6D are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 6A and 6C, respectively.

FIGS. 6E and 6F are a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 4A and 6C, respectively.

FIGS. 7A-7C illustrate fabrication of the semiconductor structure of FIG. 6A in accordance with some embodiments of the present disclosure.

FIGS. 8A-8D illustrate fabrication of the semiconductor structure of FIG. 6C in accordance with some embodiments of the present disclosure.

FIGS. 9A and 9C are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 9B and 9D are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 9A and 9C, respectively.

FIGS. 10A-10C illustrate fabrication of the semiconductor structure of FIG. 9C in accordance with some embodiments of the present disclosure.

FIGS. 11A and 11C are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 11B and 11D are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 11A and 11C, respectively.

FIGS. 12A, 12C and 12E are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 12B, 12D and 12F are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 12A, 12C and 12E, respectively.

FIGS. 13A-13C illustrate fabrication of the semiconductor structure of FIG. 12C in accordance with some embodiments of the present disclosure.

FIGS. 14A-14D illustrate fabrication of the semiconductor structure of FIG. 12E in accordance with some embodiments of the present disclosure.

FIGS. 15A and 15C are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 15B and 15D are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 15A and 15C, respectively.

FIGS. 16A-16C illustrate fabrication of the semiconductor structure of FIG. 15C in accordance with some embodiments of the present disclosure.

FIGS. 17A and 17C are examples of semiconductor structures in accordance with some embodiments of the present disclosure.

FIGS. 17B and 17D are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 17A and 17C, respectively.

FIGS. 17E and 17F are a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structures in FIGS. 17A and 17C, respectively.

FIG. 18 is a flow chart diagram of a method of fabricating a semiconductor structure according to various aspects of the present disclosure.

FIGS. 19-21 illustrate schematic cross-sectional views of the semiconductor structure associated with the method of FIG. 18 in accordance with some embodiments of the present disclosure.

FIGS. 22-56 illustrate schematic cross-sectional views of the semiconductor structure in accordance with some embodiments of the present disclosure.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, or examples, for implementing different features of the provided subject matter. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. For example, the formation of a first feature over or on a second feature in the description that follows may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed between the first and second features, such that the first and second features may not be in direct contact. In addition, the present disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The apparatus may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein may likewise be interpreted accordingly.

The following embodiments disclose ferroelectric or antiferroelectric capacitor structures that can be used for negative-capacitance fin field effect transistors (NC-FinFETs) with subthreshold swing improvement.

As the transistor size is scaled down, continuously scaling down of voltage (e.g., power supply) is a target for ultra-low power devices. However, voltage scaling down will meet the bottleneck of physical limitation of subthreshold swing with 60 mV/decade, which is accompanied with a higher off-state leakage current. An NC-FET, which introduces negative capacitance to a gate stack of MOSFET, will overcome the problem. The negative-capacitance may result from the ferroelectricity or antiferroelectricity of a dielectric layer in the gate stack.

Reference is made to FIGS. 1A and 1B. FIGS. 1A and 1B are diagrams showing energy versus polarization for ferroelectricity and antiferroelectricity, respectively. As shown in FIG. 1A, materials with ferroelectricity possess two or more stable states of different nonzero polarization and thus exhibit nonzero polarization without an applied electric field. As a result, materials with ferroelectricity are able to be switched between those different polarization states by an applied electric field. In contrast, as shown in FIG. 1B, materials with antiferroelectricity possess a stable state of zero polarization (nonpolar AFE phase) and two metastable states of nonzero polarization (polar FE phase), and hence exhibit no polarization without an applied electric field. However, antiferroelectric materials are able to be switched to one of the two original metastable states of nonzero polarization (AFE phase->FE phase) when an electric field is applied. Once the applied electric field is removed, such materials are switched back to the stable state of zero polarization (FE phase->AFE phase).

With reference to FIGS. 2A-3B. FIG. 2A is a diagram showing transient currents during an electric field with a triangular-shaped wave in which Ec is coercive field. FIG. 2B is a diagram showing an alternating current (AC) excitation signal, which is expressed as E(t), a function of time. FIG. 2C is a diagram showing an exemplary polarization-electric field (P-E) hysteresis loop of a ferroelectric material in which Pr is remanent polarization and Ec is coercive field. FIG. 3A is a diagram showing current density versus electric field of antiferroelectric materials. The label “AFE-FE” in the figure indicates that the switching peak arises from the transformation of a non-polar antiferroelectric phase into a polar ferroelectric phase. FIG. 3B is a diagram showing polarization versus electric field of an antiferroelectric material. Ferroelectricity or antiferroelectricity may be measured using a dynamic hysteresis measurement with a triangular excitation field, which has a triangular wave form (see FIG. 2B), and by integrating the current with time, the polarization may be obtained. When a material that exhibits ferroelectricity or antiferroelectricity undergoes switching between different polarization states, it gives rise to a switching current and a sudden change in polarization, which corresponds to a peak in the transient current-electric field (I-E) loop (see FIGS. 2A and 3A) and a steep slope in the polarization-electric field (P-E) hysteresis loop (see FIGS. 2C and 3B), respectively. There is an energy barrier to overcome for the switching process to take place, and thus the switching process happens when the excitation field exceeds a threshold value, which results in the hysteric behavior in the P-E loop of the material exhibiting ferroelectricity or antiferroelectricity.

Once a positive triangular excitation field is applied across a material that exhibits ferroelectricity, one switching operation occurs if the ascending field exceeds a threshold value, which is also referred to as coercive field (Ec), and this corresponds to the switching of the stable state from a positive polarization to a negative polarization. The same goes for a negative triangular excitation field but of the opposite sign. Such a ferroelectricity shows an I-E loop (see FIG. 2A) with two peaks and a single hysteretic P-E loop (see FIG. 2C).

In comparison, in the case of a material that exhibits antiferroelectricity, two switching operations occur when a positive triangular excitation field is applied. The first switching takes place when the ascending field exceeds one threshold value (E_(F)) and the material undergoes a switching from its non-polar state (AFE phase) into a positive polarization state (FE phase). This switching process is referred to as “field-induced-phase-transition” of an antiferroelectric material. The second switching takes place when the descending field reduces to another threshold value (E_(A)) less than the previous threshold value (E_(F)) and the material switches from its polar state (FE phase) to its non-polar state (AFE phase) (see FIG. 3B). Again, the same goes for a negative triangular excitation field but of opposite sign. Therefore, the material which exhibits antiferroelectricity has an I-E loop with four peaks (see FIG. 3A) and a double hysteresis P-E loops (see FIG. 3B).

Modulation of ferroelectricity or antiferroelectricity of a zirconium-containing oxide material is provided, which will be discussed in more detail below. Corresponding hysteresis loops are illustrated, as shown in FIGS. 4B, 4C, 4E, 6B, 6D-6F, 9B, 9D, 11B, 11D, 12B, 12D, 12F, 15B, 15D, 17B, 17D-17F where first curves 4P1, 4P2, 4P3, 6P1, 6P2, 6P3, 6P4, 9P1, 9P2, 11P1, 11P2, 12P1, 12P2, 12P3, 15P1, 15P2, 17P1, 17P2, 17P3 and 17P4 are depicted. The first curves are given in terms of the polarization charge in microcoulombs per squared centimeter versus the electric field in microvolts per centimeter, as for example, first curve 4P1 in FIG. 4B. Corresponding transient current-electric field (I-E) loops to ferroelectric structures are also illustrated in FIGS. 4B, 4C, 4E, 6B, 6D-6F, 9B, 9D, 11B, 11D, 12B, 12D, 12F, 15B, 15D, 17B, 17D-17F where second curves 4J1, 4J2, 4J3, 6J1, 6J2, 6J3, 6J4, 9J1, 9J2, 11J1, 11J2, 12J1, 12J2, 12J3, 15J1, 15J2, 17J1, 17J2, 17J3 and 17J4 are depicted. The second curves are given in terms of the current density in microamperes per squared micrometer versus the electric field in microvolts per centimeter, as for example, second curve 4J1 in FIG. 4B.

FIG. 4A is an example of a semiconductor structure 1 in accordance with some embodiments. As shown in FIG. 4A, a bottom electrode 104, a ZrO₂ layer 106 and a top electrode 108 are sequentially formed over a substrate 102. The bottom electrode 104, the ZrO₂ layer 106, and the top electrode 108, in combination, serve as a metal-insulator-metal (MIM) capacitor, wherein the bottom and top electrodes 104 and 108 are metal layers of the MIM capacitor, and the ZrO₂ layer 106 is a dielectric layer between the metal layers and has ferroelectricity or antiferroelectricity. In some embodiments, the bottom electrode 104 and/or top electrode 108 are made of Pt or other suitable metals. In some embodiments, the substrate 102 is made of silicon or other suitable semiconductors. The substrate 102 may be a silicon substrate with a p-type dopant (e.g., boron), for example.

The voltage across the MIM capacitor formed by the bottom electrode 104, a ZrO₂ layer 106, and a top electrode 108 is calculated from the equation derived from the Landua model for ferroelectrics: V=(2αQ+4βQ³)*T, where α and β are anisotropy constant, Q is the surface charge density and T is the ferroelectric (or antiferroelectric) layer thickness. When imposing a voltage on the MIM capacitor, the voltage is amplified due to the induced negative voltage across the ferroelectric MIM capacitor, resulting in a sub-60 mV/decade subthreshold swing when the MIM capacitor is used in a transistor (i.e., NC-FET).

FIGS. 4B and 4C are charts of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 1 having different ZrO₂ layer thicknesses. In greater detail, the chart as shown in FIG. 4B corresponds to the semiconductor structure 1 with a ZrO₂ layer 106 having a thickness of about 10.3 nm, and the chart as shown in FIG. 4C corresponds to the semiconductor structure 1 with the ZrO₂ layer 106 having a thickness of about 6.4 nm. Comparing curves 4P1, 4J1 in FIG. 4B with curves 4P2, 4J2 in FIG. 4C, the ZrO₂ layer 106 having a thickness of about 6.4 nm exhibits weaker ferroelectricity (e.g., smaller remanent polarization and wider distribution of the switching field) than that of the ZrO₂ layer 106 having a thickness of about 10.3 nm. Therefore, scaling down of the ZrO₂ layer 106 would result in weakened ferroelectricity, as shown in FIGS. 4B and 4C.

FIG. 4D shows another semiconductor structure 2 similar to the semiconductor structure 1, except for a seed layer 110 between the bottom electrode 104 and the ZrO₂ layer 106. In greater detail, the semiconductor structure 2 includes the seed layer 110 which is made of HfO₂ and under the ZrO₂ layer 106 having the thickness of 6.4 nm. FIG. 4E is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 2. Comparing curves 4P3, 4J3 in FIG. 4E with curves 4P2, 4J2 in FIG. 4C, the ferroelectricity and the hysteresis behavior of the semiconductor structure 2 are enhanced (e.g., larger remanent polarization and narrower distribution of the switching field) as compared to the semiconductor structure 1 without the seed layer. Based on FIGS. 4B, 4C and 4E, it can be concluded that a thin ZrO₂ layer (with a thickness less than 10 nm) has unsatisfactory ferroelectricity, but a combined structure of an HfO₂ seed layer and the thin ZrO₂ layer deposited directly on the HfO₂ seed layer has an improved ferroelectricity. Moreover, the seed layer 110 has a thickness less than the ZrO₂ layer 106, so that a thickness of the combined structure of the layers 110 and 106 can be thin enough to meet satisfaction of scaling down. In some embodiments, the thickness of the seed layer 110 is in a range from about 1 nm to about 5 nm. For example, the seed layer 110 resulting in the chart shown in FIG. 4E has a thickness of about 2.3 nm.

FIGS. 5A-5C illustrate fabrication of the semiconductor structure 2 of FIG. 4D in accordance with some embodiments of the present disclosure. As shown in FIG. 5A, the bottom electrode 104 is formed over the substrate 102, and the seed layer 110 is formed over the bottom electrode 104. In some embodiments, the bottom electrode 104 is made of Pt or other suitable conductive materials, and is formed using a suitable method such as plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof.

In some embodiments where the seed layer 110 includes HfO₂, the HfO₂ seed layer 110 may be formed by plasma-enhanced atomic layer deposition (PEALD) utilizing a process temperature range from about 270° C. to about 500° C. If the process temperature is higher than about 500° C., the seed layer 110 may intermix with underlying materials (e.g., materials of the bottom electrode 104 and the substrate 102) due to interdiffusion of atoms at high temperature. If the process temperature is lower than about 270° C., the seed layer 110 may contain defects such as oxygen vacancies that will in turn degrade the performance and reliability of the ferroelectric devices. For example, the PEALD process uses tetrakis dimethyl amino hafnium (TDMAH or Hf[N(CH₃)₂]₄) and oxygen plasma as precursors for hafnium and oxygen, respectively.

As shown in FIG. 5B, the ZrO₂ layer 106 is formed over the as-deposited seed layer 110 using a suitable method, for example, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof. In some embodiments, the ZrO₂ layer 106 may be formed by PEALD utilizing a process temperature range from about 270° C. to about 500° C. If the process temperature is higher than about 500° C., the seed layer 110 may intermix with ZrO₂ layer 106 due to interdiffusion of atoms at high temperature. If the process temperature is lower than about 270° C., the ZrO₂ layer 106 may be formed into crystalline phases that that will not contribute to ferroelectricity. For example, the PEALD process uses tetrakis(dimethylamino)zirconium (TDMAZ or Zr[N(CH₃)₂]₄) and oxygen plasma as precursors for zirconium and oxygen, respectively.

Deposition of the seed layer 110 and deposition of the ZrO₂ layer 106 are controlled such that the seed layer 110 has a thickness less than a thickness of the ZrO₂ layer 106, which in turn will be advantageous for scaling down the semiconductor structure 2 as well as improving the ferroelectricity of the ZrO₂ layer 106. For example, the seed layer 110 can be deposited on the bottom electrode 104 using ALD, and the resulting seed layer 110 has a thickness in a range from about 1 nm to about 5 nm. Moreover, the ZrO₂ layer 106 can be deposited on the seed layer 110 using ALD, and the ZrO₂ layer 106 has a thickness in a range from about 6.4 nm to about 10 nm.

As shown in FIG. 5C, the top electrode 108 is formed over the ZrO₂ layer 106. The top electrode 108 and the bottom electrode 104 may include the same material in some embodiments. For example, the top electrode 108 is made of Pt or other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process. The deposition process includes chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof. The patterning process includes suitable lithography and etching techniques.

FIG. 6A shows another semiconductor structure 3 similar to the semiconductor structure 2, except for a seed layer 112 made of TiO₂, instead of HfO₂. In greater detail, the semiconductor structure 3 includes the ZrO₂ layer 106 and the TiO₂ seed layer 112 over the ZrO₂ layer 106. The ZrO₂ layer 106 has a thickness of about 6.4 nm, and the TiO₂ seed layer 112 has a thickness of about 4.5 nm. FIG. 6B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 3. The curves 6P1 and 6J1 in FIG. 6B show that a ferroelectric to antiferroelectric phase transition is induced in the ZrO₂ layer 106 by incorporating the TiO₂ seed layer 112. Therefore, the ZrO₂ layer 106 with the underlying TiO₂ seed layer 112 exhibits antiferroelectricity.

FIG. 6C shows another semiconductor structure 4 similar to the semiconductor structure 3, except for a capping layer 114 between the ZrO₂ layer 106 and the top electrode 108. In greater detail, the semiconductor structure 4 includes the capping layer 114 made of TiO₂ and having a thickness of about 2.7 nm. Moreover, the thickness of the TiO₂ seed layer 112 in the semiconductor structure 4 is substantially the same as the thickness of the TiO₂ capping layer 114. For example, the thickness of the TiO₂ seed layer 112 is about 2.7 nm. FIG. 6D is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 4. The curves 6P2 and 6J2 in FIG. 6D show that a ferroelectric to antiferroelectric phase transition is induced in the ZrO₂ layer 106 by incorporating the TiO₂ capping layer. Stated differently, the ZrO₂ layer 106 between two TiO₂ layers 112 and 114 can exhibit antiferroelectricity.

FIG. 6E is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to another example of the semiconductor structure 1 shown in FIG. 4A. In greater detail, the semiconductor structure 1 associated with the chart of FIG. 6E includes the ZrO₂ layer having a thickness of about 12 nm. FIG. 6F is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to another example of the semiconductor structure 4. In greater detail, the semiconductor structure 4 associated with FIG. 6F includes the ZrO₂ layer having a thickness of about 12 nm, the TiO₂ seed layer 112 having a thickness of about 5.7 nm, and the TiO₂ capping layer 114 having a thickness of about 5.7 nm. Comparing curves 6P3, 6J3 in FIG. 6E with curves 6P4, 6J4 in FIG. 6F, when the ZrO₂ layer has a thickness of about 12 nm, the TiO₂ seed layer having a thickness of about 5.7 nm and TiO₂ capping layer having a thickness of about 5.7 nm can enhance the ferroelectricity and the hysteresis behavior.

FIGS. 7A-7C illustrate fabrication of the semiconductor structure 3 of FIG. 6A in accordance with some embodiments of the present disclosure. As shown in FIG. 7A, the bottom electrode 104 is formed over the substrate 102, and the seed layer 112 is formed over the bottom electrode 104. In some embodiments, the bottom electrode 104 is made of Pt or other suitable conductive materials, and is formed using a suitable method, as discussed previously with respect to FIG. 5A.

In some embodiments where the seed layer 112 includes TiO₂, the TiO₂ seed layer 112 may be formed by PEALD utilizing a process temperature range from about 270° C. to about 500° C. If the process temperature is higher than about 500° C., the seed layer 112 may intermix with underlying materials (e.g., materials of the bottom electrode 104 and the substrate 102) due to interdiffusion of atoms at high temperature. If the process temperature is lower than about 270° C., the seed layer 112 may contain defects such as oxygen vacancies that will in turn degrade the performance and reliability of the ferroelectric devices. For example, in some embodiments, the PEALD process uses tetrakis-dimethyl-amino-titanium (TDMAT or Ti[N(CH₃)₂]₄), titanium tetrachloride (TiCl₄), titanium methoxide (Ti(OMe)₄ where Me is a methyl group) as a precursor for titanium, and uses oxygen plasma as a precursor for oxygen.

As shown in FIG. 7B, the ZrO₂ layer 106 is formed over the as-deposited TiO₂ seed layer 112 using a suitable method, as discussed previously with respect to FIG. 5B.

Deposition of the TiO₂ seed layer 112 and deposition of the ZrO₂ layer 106 are controlled such that the TiO₂ seed layer 112 has a thickness less than a thickness of the ZrO₂ layer 106, which in turn will be advantageous for scaling down the semiconductor structure 3 as well as improving the ferroelectricity.

As shown in FIG. 7C, the top electrode 108 is formed over the ZrO₂ layer 106. The top electrode 108 and the bottom electrode 104 may include the same material in some embodiments. For example, the top electrode 108 is made of Pt or other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIGS. 8A-8D illustrate fabrication of the semiconductor structure 4 of FIG. 6C in accordance with some embodiments of the present disclosure. As shown in FIG. 8A, the bottom electrode 104 is formed over the substrate 102, and the seed layer 112 is formed over the bottom electrode 104. In some embodiments, the bottom electrode 104 is made of Pt or other suitable conductive materials, and is formed using a suitable method, as discussed previously with respect to FIG. 5A.

In some embodiments where the seed layer 112 includes TiO₂, the TiO₂ seed layer 112 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 7A.

As shown in FIG. 8B, the ZrO₂ layer 106 is formed over the TiO₂ seed layer 112 using a suitable method, as discussed previously with respect to FIG. 5B.

As shown in FIG. 8C, the capping layer 114 is then formed over the ZrO₂ layer 106. In some embodiments where the capping layer 114 includes TiO₂, the deposition condition (e.g., temperature and/or precursors) of the capping layer 114 is substantially the same as that of the TiO₂ seed layer 112. For example, the TiO₂ capping layer 114 may be formed by PEALD utilizing a process temperature range from about 270° C. to about 500° C. If the process temperature is higher than about 500° C., the TiO₂ capping layer 114 may intermix with the ZrO₂ layer 106 due to interdiffusion of atoms at high temperature. If the process temperature is lower than about 270° C., the TiO₂ capping layer 114 may contain defects such as oxygen vacancies that will in turn degrade the performance and reliability of the ferroelectric devices. For example, in some embodiments, the PEALD process uses tetrakis-dimethyl-amino-titanium (TDMAT or Ti[N(CH₃)₂]₄), titanium tetrachloride (TiCl₄), titanium methoxide (Ti(OMe)₄ where Me is a methyl group) as a precursor for titanium, and uses oxygen plasma as a precursor for oxygen.

As shown in FIG. 8D, the top electrode 108 is formed over the TiO₂ capping layer 114. The top electrode 108 and the bottom electrode 104 may include the same material in some embodiments. For example, the top electrode 108 is made of Pt or other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIG. 9A shows another semiconductor structure 5 similar to the semiconductor structure 1, except for the bottom electrode 105 made of TiN, instead of Pt. In greater detail, the semiconductor structure 5 includes the ZrO₂ layer 106 deposited on the TiN bottom electrode 105 and having a thickness of about 6.4 nm. FIG. 9B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric filed (I-E) loop with respect to the semiconductor structure 5.

FIG. 9C shows another semiconductor structure 6 similar to the semiconductor structure 5, except for the capping layer 114 between the ZrO₂ layer 106 and the top electrode 108. In greater detail, the semiconductor structure 6 includes the ZrO₂ layer 106 and the capping layer 114 over the ZrO₂ layer 106. The ZrO₂ layer 106 has a thickness of about 6.4 nm. The capping layer 114 is made of TiO₂ and has a thickness of about 5.7 nm. FIG. 9D is a chart of a polarization-electric field (P-E) loop with respect to the semiconductor structure 6. Comparing curves 9P1, 9J1 in FIG. 9B with curves 9P2, 9J2 in FIG. 9D, by incorporating the TiO₂ capping layer 114, the antiferroelectricity and the hysteresis behavior of the semiconductor structure 6 are enhanced as compared to the semiconductor structure 5 without the TiO₂ capping layer 114.

FIGS. 10A-10C illustrate fabrication of the semiconductor structure 6 of FIG. 9C in accordance with some embodiments of the present disclosure. As shown in FIG. 10A, the bottom electrode 105 is formed over the substrate 102, and the ZrO₂ layer 106 is formed over the bottom electrode 104. In this embodiment, the bottom electrode 105 is made of TiN and formed using a suitable method such as plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof.

As shown in FIG. 10A, the ZrO₂ layer 106 is formed over the bottom electrode 105 using a suitable method, as discussed previously with respect to FIG. 5B.

As shown in FIG. 10B, the capping layer 114 is formed over the ZrO₂ layer 106. In some embodiments where the capping layer 114 includes TiO₂, the TiO₂ capping layer 114 may be formed by PEALD, as discussed previously with respect to FIG. 8C.

Deposition of the TiO₂ capping layer 114 and deposition of the ZrO₂ layer 106 are controlled such that the TiO₂ capping layer 114 has a thickness less than a thickness of the ZrO₂ layer 106, which in turn will be advantageous for scaling down the semiconductor structure 6 as well as improving the antiferroelectricity of the ZrO₂ layer 106. For example, the capping layer 114 and the ZrO₂ layer 106 can be deposited using ALD, the resulting capping layer 114 has a thickness in a range from about 1 nm to about 6 nm, and the ZrO₂ layer 106 has a thickness greater than 6 nm.

As shown in FIG. 10C, the top electrode 108 is formed over the capping layer 114. The top electrode 108 may include different material than the bottom electrode 105. For example, the top electrode 108 includes Pt and the bottom electrode 105 includes TiN. In other embodiments, the top electrode 108 may include same material as the bottom electrode 105. For example, the top electrode 108 includes TiN and the bottom electrode 105 also includes TiN. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIG. 11A shows another semiconductor structure 7 similar to the semiconductor structure 1, except for omitting the bottom electrode 104. In greater detail, the semiconductor structure 7 includes a substrate 102 a with heavily doped p-type dopants (e.g., boron) in contact with a bottom surface of the ZrO₂ layer 106. The heavily doped substrate 102 a can act as a conductor and thus serve as a bottom electrode due to the heavy dopant concentration. In some embodiments, the ZrO₂ layer 106 has a thickness of about 6.4 nm. FIG. 11B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 7. The curves 11P1 and 11J1 in FIG. 11B show that the ZrO₂ layer 106 in contact with the heavily doped substrate 102 a exhibits a paraelectric characteristic.

FIG. 11C shows another semiconductor structure 8 similar to the semiconductor structure 7, except for the seed layer 112 between the substrate 102 a and the ZrO₂ layer 106. In some embodiments, the seed layer 112 is made of TiO₂ and has a thickness of about 2.7 nm. FIG. 11D is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 8. The curves 11P2 and 11J2 in FIG. 11D show that a paraelectric to ferroelectric phase transition is induced in the ZrO₂ layer 106 by incorporating the TiO₂ seed layer 112. That is, the TiO₂ seed layer 112 between the ZrO₂ layer 106 and the heavily doped substrate 102 a can result in ferroelectricity for the ZrO₂ layer 106.

FIG. 12A shows a semiconductor structure 9 in accordance with some embodiments. As shown in FIG. 12A, a bottom electrode 104, a Hf_(0.5)Zr_(0.5)O₂ layer 116 and a top electrode 108 are sequentially formed over a substrate 102. In some embodiments, the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness of about 11.9 nm. The bottom electrode 104, the Hf_(0.5)Zr_(0.5)O₂ layer 116, and the top electrode 108 are in combination serve as an MIM capacitor, wherein the Hf_(0.5)Zr_(0.5)O₂ layer 116 is a dielectric layer between the metal layers 104 and 108 and has ferroelectricity or antiferroelectricity. FIG. 12B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 9.

FIG. 12C shows another semiconductor structure 10 similar to the semiconductor structure 9, except for the TiO₂ seed layer 112 between the bottom electrode 104 and the Hf_(0.5)Zr_(0.5)O₂ layer 116. In greater detail, the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness of about 11.9 nm, and the TiO₂ seed layer 112 has a thickness of about 2.7 nm. FIG. 12D is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 10. Comparing curves 12P1, 12J1 in FIG. 12B with curves 12P2, 12J2 in FIG. 12D, the ferroelectricity and the hysteresis behavior of the semiconductor structure 10 with the TiO₂ seed layer 112 are enhanced as compared to the semiconductor structure 9 without the TiO₂ seed layer.

FIG. 12E shows another semiconductor structure 11 similar to the semiconductor structure 10, except for the TiO₂ capping layer 114 between the Hf_(0.5)Zr_(0.5)O₂ layer 116 and the top electrode 108. In greater detail, the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness of about 11.9 nm, the TiO₂ seed layer 112 has a thickness of about 2.7 nm, and the TiO₂ capping layer 114 has a thickness of about 2.7 nm. FIG. 12F is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 11. Comparing curves 12P1, 12J1 in FIG. 12B with curves 12P3, 12J3 in FIG. 12F, the ferroelectricity and the hysteresis behavior of the semiconductor structure 11 with the TiO₂ capping layer 114 and the TiO₂ seed layer 112 are enhanced as compared to the semiconductor structure 9 without the TiO₂ capping and seed layers.

FIGS. 13A-13C illustrate fabrication of the semiconductor structure 10 of FIG. 12C in accordance with some embodiments of the present disclosure. As shown in FIG. 13A, the bottom electrode 104 is formed over the substrate 102, and the seed layer 112 is formed over the bottom electrode 104. In some embodiments, the bottom electrode 104 is made of Pt or other suitable conductive materials, and is formed using a suitable method, as discussed previously with respect to FIG. 5A.

In some embodiments where the seed layer 112 includes TiO₂, the TiO₂ seed layer 112 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 7A.

As shown in FIG. 13B, the Hf_(0.5)Zr_(0.5)O₂ layer 116 is formed over the as-deposited seed layer 112 using a suitable method, for example, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof. In some embodiments, the Hf_(0.5)Zr_(0.5)O₂ layer 116 may be formed by PEALD utilizing a process temperature range from about 270° C. to about 500° C. If the process temperature is higher than about 500° C., the Hf_(0.5)Zr_(0.5)O₂ layer 116 may be formed into crystalline phases that will not contribute to ferroelectricity. If the process temperature is lower than about 270° C., the Hf_(0.5)Zr_(0.5)O₂ layer 116 will not have sufficient crystallinity to show ferroelectric properties. For example, in some embodiments, the PEALD process uses tetrakis(dimethylamino)zirconium (TDMAZ, Zr[N(CH₃)₂]₄) as a precursor for zirconium, tetrakis dimethyl amino hafnium (TDMAH or Hf[N(CH₃)₂]₄) as a precursor for hafnium, and oxygen plasma as a precursor for oxygen.

Deposition of the TiO₂ seed layer 112 and deposition of the Hf_(0.5)Zr_(0.5)O₂ layer 116 are controlled such that the seed layer 112 has a thickness less than a thickness of the Hf_(0.5)Zr_(0.5)O₂ layer 116, which in turn will be advantageous for scaling down the semiconductor structure 10 as well as improving the ferroelectricity. For example, the seed layer 112 and the bottom electrode 104 can be deposited using ALD, and the resulting seed layer 112 has a thickness in a range from about 1 nm to about 5 nm, and the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness in a range from about 5 nm to about 12 nm.

As shown in FIG. 13C, the top electrode 108 is formed over the Hf_(0.5)Zr_(0.5)O₂ layer 116. The top electrode 108 and the bottom electrode 104 may include the same material in some embodiments. For example, the top electrode 108 includes or is made of Pt or other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIGS. 14A-14D illustrate fabrication of the semiconductor structure 11 of FIG. 12E in accordance with some embodiments of the present disclosure. As shown in FIG. 14A, the bottom electrode 104 is formed over the substrate 102, and the seed layer 112 is formed over the bottom electrode 104. In some embodiments, the bottom electrode 104 is made of Pt or other suitable conductive materials, and is formed using a suitable method, as discussed previously with respect to FIG. 5A.

In some embodiments where the seed layer 112 includes TiO₂, the TiO₂ seed layer 112 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 7A.

As shown in FIG. 14B, the Hf_(0.5)Zr_(0.5)O₂ layer 116 is formed over the as-deposited seed layer 112 using PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 13B.

As shown in FIG. 14C, the capping layer 114 is formed over the Hf_(0.5)Zr_(0.5)O₂ layer 116. In some embodiments where the capping layer 114 includes TiO₂, the TiO₂ capping layer 114 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 8C.

Deposition of the seed layer 112, capping layer 114 and deposition of the Hf_(0.5)Zr_(0.5)O₂ layer 116 are controlled such that the TiO₂ seed layer 112 and the TiO₂ capping layer 114 have thicknesses less than a thickness of the Hf_(0.5)Zr_(0.5)O₂ layer 116, which in turn will be advantageous for scaling down the semiconductor structure 11 as well as improving the ferroelectricity.

As shown in FIG. 14D, the top electrode 108 is formed over TiO₂ capping layer 114. The top electrode 108 and the bottom electrode 104 may include the same material in some embodiments. For example, the top electrode 108 is made of Pt or other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIG. 15A shows another semiconductor structure 12 similar to the semiconductor structure 9, except for the bottom electrode 105 made of TiN, instead of Pt. FIG. 15B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 12.

FIG. 15C shows another semiconductor structure 13 similar to the semiconductor structure 12, except for the TiO₂ capping layer 114 between the Hf_(0.5)Zr_(0.5)O₂ layer 116 and the top electrode 108. In some embodiments, the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness of about 11.9 nm, and the TiO₂ capping layer 114 has a thickness of about 2.7 nm. FIG. 15D is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to semiconductor structure 13. Comparing curves 15P1, 15J1 in FIG. 15B with curves 15P2, 15J2 in FIG. 15D, the ferroelectricity and the hysteresis behavior of the semiconductor structure 13 with the TiO₂ capping layer 114 are enhanced as compared to the semiconductor structure 12 without the TiO₂ capping layer.

FIGS. 16A-16C illustrate fabrication of the semiconductor structure 13 of FIG. 15C in accordance with some embodiments of the present disclosure. As shown in FIG. 16A, the bottom electrode 105 is formed over the substrate 102. In some embodiments, the bottom electrode 105 is made of TiN and formed using a suitable method such as plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), and/or combinations thereof.

The Hf_(0.5)Zr_(0.5)O₂ layer 116 is formed over the TiN bottom electrode 105 using PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 13B.

As shown in FIG. 16B, the capping layer 114 is formed over the Hf_(0.5)Zr_(0.5)O₂ layer 116. In some embodiments where the capping layer 114 includes TiO₂, the TiO₂ capping layer 114 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 8C.

Deposition of the TiO₂ capping layer 114 and deposition of the Hf_(0.5)Zr_(0.5)O₂ layer 116 are controlled such that the TiO₂ capping layer 114 have thicknesses less than a thickness of the Hf_(0.5)Zr_(0.5)O₂ layer 116, which in turn will be advantageous for scaling down the semiconductor structure 13 as well as improving the ferroelectricity.

As shown in FIG. 16C, the top electrode 108 is formed over the TiO₂ capping layer 114. The top electrode 108 and the bottom electrode 105 may include the same material in some embodiments. For example, the top electrode 108 is made of TiN and the bottom electrode 105 is made of TiN. In other embodiments, the top electrode 108 may include different material than the bottom electrode 105. For example, the top electrode 108 includes Pt and the bottom electrode 105 includes TiN. In other embodiments, the top electrode 108 may include other suitable conductive materials. The top electrode 108 is formed using a deposition process, followed by a patterning process, as discussed previously with respect to FIG. 5C.

FIG. 17A shows another semiconductor structure 14 similar to the semiconductor structure 12 shown in FIG. 15A, except for omitting the bottom electrode 105. In greater detail, the semiconductor structure 14 includes the substrate 102 a with heavily doped p-type dopants (e.g., boron) in contact with a bottom surface of the Hf_(0.5)Zr_(0.5)O₂ layer 116. The heavily doped substrate 102 a can act as a conductor and thus serve as a bottom electrode due to the heavy dopant concentration. In some embodiments, the Hf_(0.5)Zr_(0.5)O₂ layer 116 has a thickness of about 11.9 nm. FIG. 17B is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 14.

FIG. 17C shows another semiconductor structure 15 similar to the semiconductor structure 14, except for the TiO₂ seed layer 112 made of TiO₂ and the TiO₂ capping layer 114 on opposite sides of the Hf_(0.5)Zr_(0.5)O₂ layer 116. In greater detail, the TiO₂ seed and capping layers 112 and 114 have substantially the same thickness (e.g., about 2.7 nm). FIG. 17D is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to the semiconductor structure 15. Comparing curves 17P1, 17J1 in FIG. 17B with curves 17P2, 17J2 in FIG. 17D, the ferroelectricity and the hysteresis behavior of the semiconductor structure 15 with TiO₂ seed and capping layers 112 and 114 are enhanced as compared to the semiconductor structure 14 without TiO₂ seed and capping layers.

FIG. 17E is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to another example of the semiconductor structure 14. In greater detail, the semiconductor structure 14 associated with the chart of FIG. 17E includes the Hf_(0.5)Zr_(0.5)O₂ layer 116 having a thickness of about 7 nm. The curves 17P3 and 17J3 in FIG. 17E show that the Hf_(0.5)Zr_(0.5)O₂ layer 116 with 7 nm thickness and in contact with heavily doped substrate 102 a exhibits a paraelectric characteristic. FIG. 17F is a chart of a polarization-electric field (P-E) hysteresis loop overlying a transient current-electric field (I-E) loop with respect to another example of the semiconductor structure 15. In greater detail, the semiconductor structure 15 associated with FIG. 17F includes the Hf_(0.5)Zr_(0.5)O₂ layer 116 having a thickness of about 7 nm, the TiO₂ seed layer 112 having a thickness of about 2.7 nm, and the TiO₂ capping layer 114 having a thickness of about 2.7 nm. Comparing curves 17P3, 17J3 in FIG. 17E with curves 17P4, 17J4 in FIG. 17F, a paraelectric to ferroelectric phase transition is induced in the Hf_(0.5)Zr_(0.5)O₂ layer 116 due to the TiO₂ layers 112 and 114 on opposite sides of the Hf_(0.5)Zr_(0.5)O₂ layer 116.

Based on the above discussion, it can be seen that the ferroelectricity or antiferroelectricity of the zirconium-containing oxide layer (e.g., ZrO₂ layer or Hf_(0.5)Zr_(0.5)O₂ layer) can be enhanced or otherwise modified by forming a zirconium-free metal oxide layer (e.g., HfO₂ or TiO₂ layer) in contact with a bottom surface and/or a top surface of the zirconium-containing oxide layer. Moreover, the thickness of the zirconium-free metal oxide layer can be less than the thickness of the zirconium-containing oxide layer, so as to facilitate scaling down the semiconductor structure. Furthermore, because the ferroelectricity or antiferroelectricity can be satisfied by incorporating the zirconium-free metal oxide layer, annealing or other thermal treatment to the as-deposited zirconium-containing oxide layer for improving the ferroelectricity or antiferroelectricity can be omitted. The concept of improving the ferroelectricity or antiferroelectricity of the zirconium-containing oxide layer by the thin zirconium-free metal oxide layer can be used in various devices, such as an NC-FET, a ferroelectric random access memory (FeRAM) device, a ferroelectric tunnel junction (FTJ) device or the like. Embodiments below are about an NC-FET employing the foregoing concept.

A field effect transistor (FET) and a method of forming the same are provided in accordance with various exemplary embodiments. The intermediate stages of forming the FET are illustrated. The variations of the embodiments are discussed. Throughout the various views and illustrative embodiments, like reference numbers are used to designate like elements.

Examples of an NCFET and a method of forming the same are described with reference to FIGS. 18-21. In particular, FIG. 18 is a flow chart diagram of a method 1000 of fabricating semiconductor structures with a negative capacitance gate stack according to various aspects of the present disclosure. Additional steps can be provided before, during, and after the method 1000, and some of the steps described can be replaced or eliminated for other embodiments of the method 1000. FIGS. 19-21 illustrate schematic cross-sectional views of the semiconductor structure corresponding to the flow chart in FIG. 18 in accordance with some embodiments.

Referring to block 1001 of FIG. 18 and to FIG. 19, the semiconductor structure 16 is received. The semiconductor structure 16 includes a substrate 102 upon which devices are to be formed. In various examples, the substrate 102 includes an elementary (single element) semiconductor, such as silicon or germanium in a crystalline structure; a compound semiconductor, such as silicon germanium, silicon carbide, gallium arsenic, gallium phosphide, indium phosphide, indium arsenide, and/or indium antimonide; a non-semiconductor material, such as soda-lime glass, fused silica, fused quartz, and/or calcium fluoride (CaF₂); and/or combinations thereof.

The substrate 102 may be uniform in composition or may include various layers. The layers may have similar or different compositions, and in various embodiments, some substrate layers have non-uniform compositions to induce device strain and thereby tune device performance. Examples of layered substrates include silicon-on-insulator (SOI) substrates 102. In some such examples, a layer of the substrate 102 may include an insulator such as a semiconductor oxide, a semiconductor nitride, a semiconductor oxynitride, a semiconductor carbide, and/or other suitable insulator materials. In some embodiments, the substrate 102 may also include various p-type doped regions and/or n-type doped regions, implemented by a process such as ion implantation and/or diffusion.

The semiconductor structure 16 includes a gate dielectric layer 118 formed over the substrate 102. The gate dielectric layer 118 is made of oxide, such as silicon oxide in some embodiments. In other embodiments, the gate dielectric layer 118 includes one or more high-k dielectric layers (e.g., having a dielectric constant greater than 3.9). For example, the one or more gate dielectric layers 118 may include one or more layers of a metal oxide or a silicate of Hf, Al, Zr, combinations thereof, and multi-layers thereof. Other suitable materials include La, Mg, Ba, Ti, Pb, Zr, in the form of metal oxides, metal alloy oxides, and combinations thereof. Exemplary materials include MgO_(x), BaTi_(x)O_(y), BaSr_(x)Ti_(y)O_(z), PbTi_(x)O_(y), PbZr_(x)Ti_(y)O_(z), SiCN, SiON, SiN, Al₂O₃, La₂O₃, Ta₂O₃, Y₂O₃, HfO₂, ZrO₂, GeO₂, ZrO₂, HfZrO₂, Ga₂O₃, Gd₂O₃, TaSiO₂, TiO₂, HfSiON, YGe_(x)O_(y), YSi_(x)O_(y), LaAlO₃, and the like. The formation methods of the gate dielectric layer 118 include molecular-beam deposition (MBD), atomic layer deposition (ALD), physical vapor deposition (PVD), and the like.

A bottom electrode 104 is disposed on the gate dielectric layer 118. In some embodiments, the bottom electrode 104 serves as an internal gate or floating gate to average out a non-uniform charge in the subsequently formed layers and non-uniform potential profile along a source/drain direction. The bottom electrode 104 may be a metal selected from the group consisting of W, Cu, Ti, Ag, Al, TiAl, TiAlN, TaC, TaCN, TaSiN, Mn, Co, Pd, Ni, Re, Ir, Ru, Pt, and Zr. In some embodiments, the bottom electrode 104 includes a metal selected from the group consisting of TiN, WN, TaN, and Ru. Metal alloys such as Ti—Al, Ru—Ta, Ru—Zr, Pt—Ti, Co—Ni and Ni—Ta may be used and/or metal nitrides, such as WN_(x), TiN_(x), MoN_(x), TaN_(x), and TaSi_(x)N_(y) may be used.

Subsequently, a first seed layer 120, a first zirconium-containing oxide layer 122 and a top electrode 108 are sequentially formed over the bottom electrode 104, as shown in FIG. 19. The first seed layer 120 can be a zirconium-free metal oxide layer that is capable of enhancing or modifying ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122. Suitable materials for the first seed layer 120 may be HfO₂, TiO₂ or combinations thereof. The capability of HfO₂ or TiO₂ to enhance or modify the ferroelectricity or antiferroelectricity of zirconium-containing oxide is discussed previously with respect to FIGS. 4B, 4C, 4E, 6B, 6D-6F, 9B, 9D, 11B, 11D, 12B, 12D, 12F, 15B, 15D, 17B, and 17D-17F.

The first seed layer 120 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the first seed layer 120 includes TiO₂, the TiO₂ seed layer 120 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 7A. In some embodiments where the first seed layer 120 includes HfO₂, the HfO₂ seed layer 120 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5A. In some embodiments, the thickness of the first seed layer 120 is less than the thickness of the first zirconium-containing oxide layer 122. For example, the thickness of the first seed layer 120 is in a range from about 1 nm to about 6 nm.

In some embodiment, the first zirconium-containing oxide layer 122 is made of ZrO₂ or Hf_(0.5)Zr_(0.5)O₂. The first zirconium-containing oxide layer 122 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the first zirconium-containing oxide layer 122 includes ZrO₂, the ZrO₂ layer 122 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5B. In some embodiments where the first zirconium-containing oxide layer 120 includes Hf_(0.5)Zr_(0.5)O₂, the Hf_(0.5)Zr_(0.5)O₂ layer 122 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 13B. In some embodiments, the thickness of the first zirconium-containing oxide layer 122 is in a range from about 6 nm to about 100 nm. In some embodiments, the thickness of the first zirconium-containing oxide layer 122 is in a range from about 6 nm to about 20 nm to facilitate scaling down of the semiconductor structure 16.

The top electrode 108 may have the same material as the bottom electrode 104. Alternatively, the top electrode 108 may have a different material as the bottom electrode 104. The top electrode 108 may be formed by plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), combinations thereof, and/or other suitable techniques.

Referring to block 1003 of FIG. 18 and to FIG. 20, the gate dielectric layer 118, the bottom electrode 104, the first seed layer 120, the first zirconium-containing oxide layer 122 and the top electrode 108 are patterned using suitable lithography and etching techniques. The gate dielectric layer 118, the bottom electrode 104, the first seed layer 120, the first zirconium-containing oxide layer 122 and the top electrode 108 may be referred to as a negative capacitance gate stack of the semiconductor structure 16 because of the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122.

Referring to block 1005 of FIG. 18 and to FIG. 21, portions 124 in the substrate 102 may be doped to with an n-type dopant (e.g., phosphorus) and serve as source/drain regions 124 in some embodiments. A portion of the substrate 102 between the source/drain regions 124 may be referred to as a channel region 126. The opposing source/drain regions 124 are laterally separated by the channel region 126. The flow of carriers through the channel region 126 is controlled by a voltage applied to the top electrode 108. In some embodiments, for straining effect or other performance enhancement, the source/drain regions 124 may be formed by epitaxy growth of different semiconductor materials. For example, the substrate 102 is recessed by etching, and a semiconductor material is epitaxially grown on the recessed region with in-situ doping to form the source/drain regions 124. In alternative embodiments, the method 1000 may form the gate stack after the formation of the source/drain regions 124, such as in a gate-last procedure. For examples, a dummy gate is formed; the source/drain regions 124 are formed on sides of the dummy gate; and thereafter, the gate stack comprising layers 118, 104, 120, 122 and 108 is formed to replace the dummy gate by a gate replacement process.

Combination of the first seed layer 120 and the first zirconium-containing oxide layer 122 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120. Therefore, the semiconductor structure 16 may act as an NC-FET.

FIG. 22 shows another semiconductor structure 16 a similar to the semiconductor structure 16, except for addition of the first capping layer 128 and omission of the first seed layer 120. The first capping layer 128 is between top electrode 108 and the first zirconium-containing oxide layer 122. The first capping layer 128 can be a zirconium-free metal oxide layer that is capable of enhancing or modifying ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122. Suitable materials for the first capping layer 128 may be HfO₂, TiO₂ or combinations thereof.

The first capping layer 128 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the first capping layer 128 includes TiO₂, the TiO₂ capping layer 128 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 8C. In some embodiments where the first capping layer 128 includes HfO₂, the HfO₂ capping layer 128 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5A. In some embodiments, the thickness of the first capping layer 128 is less than the thickness of the first zirconium-containing oxide layer 122. For example, the thickness of the first capping layer 128 is in a range from about 1 nm to about 6 nm.

Combination of the first seed layer 120 and the first zirconium-containing oxide layer 122 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first capping layer 128. Therefore, the semiconductor structure 16 a can act as an NC-FET.

FIG. 23 shows another semiconductor structure 16 b similar to the semiconductor structure 16, except for the first seed layer 120 between the first zirconium-containing oxide layer 122 and the bottom electrode 104. Combination of the first seed layer 120, the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120 and the first capping layer 128. Therefore, the semiconductor structure 16 b may act as an NC-FET.

FIG. 24 shows another semiconductor structure 17 similar to the semiconductor structure 16, except for omission of the bottom electrode 104. The first seed layer 120 is in contact with the gate dielectric layer 118 due to omission of the bottom electrode 104. Combination of the first seed layer 120 and the first zirconium-containing oxide layer 122 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120. Therefore, the semiconductor structure 17 can act as an NC-FET.

FIG. 25 shows another semiconductor structure 17 a similar to the semiconductor structure 16 a, except for omission of the bottom electrode 104. Combination of the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first capping layer 128. Therefore, the semiconductor structure 17 a can act as an NC-FET.

FIG. 26 shows another semiconductor structure 17 b similar to the semiconductor structure 16 b, except for omission of the bottom electrode 104. Combination of the first seed layer 120, the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120 and the first capping layer 128. Therefore, the semiconductor structure 17 b may act as an NC-FET.

FIG. 27 shows another semiconductor structure 18 similar to the semiconductor structure 17, except for omission of the gate dielectric layer 118. The first seed layer 120 is in contact with the channel region 126 due to omission of the gate dielectric layer 118. Combination of the first seed layer 120 and the first zirconium-containing oxide layer 122 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120. Therefore, the semiconductor structure 18 may act as an NC-FET.

FIG. 28 shows another semiconductor structure 18 a similar to the semiconductor structure 17 a, except for omission of the gate dielectric layer 118. Combination of the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first capping layer 128. Therefore, the semiconductor structure 18 a can act as an NC-FET.

FIG. 29 shows another semiconductor structure 18 b similar to the semiconductor structure 17 b, except for omission of the bottom electrode 104. Combination of the first seed layer 120, the zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance. Also, the ferroelectric phase of the first zirconium-containing oxide layer 122 may be enhanced or changed to be antiferroelectric phase by the first seed layer 120 and the first capping layer 128. Therefore, the semiconductor structure 18 b may act as an NC-FET.

FIG. 30 shows another semiconductor structure 19 similar to the semiconductor structure 16, except for the middle electrode 130, the second seed layer 132 and the second zirconium-containing oxide layer 134. In greater detail, the middle electrode 130, the second seed layer 132 and the second zirconium-containing oxide layer 134 are sequentially formed over the first zirconium-containing oxide layer 122. The top electrode 108 is over the second zirconium-containing oxide layer 134. The middle electrode 130 may have the same material as the top electrode 108 and the bottom electrode 104. Alternatively, the middle electrode 130 may have a different material than the top electrode 108 and the bottom electrode 104. The middle electrode 130 may be formed by plating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), combinations thereof, and/or other suitable techniques. The middle electrode 130 may be a metal selected from the group consisting of W, Cu, Ti, Ag, Al, TiAl, TiAlN, TaC, TaCN, TaSiN, Mn, Co, Pd, Ni, Re, Ir, Ru, Pt, and Zr. In some embodiments, the bottom electrode 104 includes a metal selected from the group consisting of TiN, WN, TaN, and Ru. Metal alloys such as Ti—Al, Ru—Ta, Ru—Zr, Pt—Ti, Co—Ni and Ni—Ta may be used and/or metal nitrides, such as WN_(x), TiN_(x), MoN_(x), TaN_(x), and TaSi_(x)N_(y) may be used. The middle electrode 130 serves as an internal gate or floating gate to average out a non-uniform charge in the subsequently formed layers and non-uniform potential profile along a source/drain direction.

The second seed layer 132 can be a zirconium-free metal oxide layer that is capable of enhancing or modifying ferroelectricity or antiferroelectricity of the second zirconium-containing oxide layer 134. Suitable materials for the second seed layer 132 may be HfO₂, TiO₂ or combinations thereof. The capability of HfO₂ or TiO₂ to enhance or modify the ferroelectricity or antiferroelectricity of zirconium-containing oxide is discussed previously with respect to FIGS. 4B, 4C, 4E, 6B, 6D-6F, 9B, 9D, 11B, 11D, 12B, 12D, 12F, 15B, 15D, 17B, 17D-17F.

The second seed layer 132 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the second seed layer 132 includes TiO₂, the TiO₂ seed layer 132 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 7A. In some embodiments where the second seed layer 132 includes HfO₂, the HfO₂ seed layer 132 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5A. In some embodiments, the thickness of the second seed layer 132 is less than the thickness of the second zirconium-containing oxide layer 134. For example, the thickness of the second seed layer 132 is in a range from about 1 nm to about 6 nm.

In some embodiment, the second zirconium-containing oxide layer 134 is made of ZrO₂ or Hf_(0.5)Zr_(0.5)O₂. The second zirconium-containing oxide layer 134 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the second zirconium-containing oxide layer 134 includes ZrO₂, the ZrO₂ layer 134 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5B. In some embodiments where the second zirconium-containing oxide layer 134 includes Hf_(0.5)Zr_(0.5)O₂, the Hf_(0.5)Zr_(0.5)O₂ layer 134 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 13B. In some embodiments, the thickness of the second zirconium-containing oxide layer 134 is in a range from about 6 nm to about 100 nm. In some embodiments, the thickness of the second zirconium-containing oxide layer 134 is in a range from about 6 nm to about 20 nm to facilitate scaling down of the semiconductor structure 16.

Combination of the second zirconium-containing oxide layer 134 and the second seed layer 132 provide negative capacitance. Also, the ferroelectric phase of the second zirconium-containing oxide layer 134 may be enhanced or changed to be antiferroelectric phase by the second seed layer 132. Therefore, the semiconductor structure 19 can act as an in NC-FET.

In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other words, the first seed layer 120 and the first zirconium-containing oxide layer 122 provide ferroelectric negative capacitance (NC-FE) and the second seed layer 132 and the second zirconium-containing oxide layer 134 provide antiferroelectric negative capacitance (NC-AFE) in some embodiments. In other embodiments, the first seed layer 120 and the first zirconium-containing oxide layer 122 provide antiferroelectric negative capacitance (NC-AFE) and the second seed layer 132 and the second zirconium-containing oxide layer 134 provide ferroelectric negative capacitance (NC-FE). The stack of gate dielectric layer 118, the bottom electrode 104, the first seed layer 120, the first zirconium-containing oxide layer 122, the middle electrode 130, the second seed layer 132, the second zirconium-containing oxide layer 134 and the top electrode 108 may serve as a gate stack for an NC-FET. Such AFE-FE hybrid NC-FET can tune the threshold of steep slope Landau switches and enable achieving the steep sub-threshold to achieve high I_(on) (on-current) of the NC-FET.

In some embodiments, the ferroelectricity or antiferroelectricity of the zirconium-containing oxide layers 122 and 134 can be achieved by choosing suitable materials of the zirconium-containing oxide layers 122 and 134 and suitable materials of the associated seed layers 120 and 132, as discussed previously with respect to FIGS. 4B, 4C, 4E, 6B, 6D-6F, 9B, 9D, 11B, 11D, 12B, 12D, 12F, 15B, 15D, 17B, and 17D-17F.

FIG. 31 shows another semiconductor structure 19 a similar to the semiconductor structure 19, except for addition of a second capping layer 136 and omission of the second seed layer 132. In greater detail, the second capping layer 136 is between the top electrode 108 and the second zirconium-containing oxide layer 134. The second capping layer 136 can be a zirconium-free metal oxide layer that is capable of enhancing or modifying ferroelectricity or antiferroelectricity of the second zirconium-containing oxide layer 134. Suitable materials for the second capping layer 136 may be HfO₂, TiO₂ or combinations thereof.

The second capping layer 136 may be formed by any suitable technique, such as chemical vapor deposition (CVD), ALD, plasma enhanced CVD (PECVD), or plasma enhanced ALD (PEALD). In some embodiments where the second capping layer 136 includes TiO₂, the TiO₂ capping layer 136 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 8C. In some embodiments where the second capping layer 136 includes HfO₂, the HfO₂ capping layer 136 may be formed by PEALD at a suitable temperature using suitable precursors, as discussed previously with respect to FIG. 5A. In some embodiments, the thickness of the second capping layer 136 is less than the thickness of the second zirconium-containing oxide layer 134. For example, the thickness of the second capping layer 136 is in a range from about 1 nm to about 6 nm. Combination of the second zirconium-containing oxide layer 134 and the second capping layer 136 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the second zirconium-containing oxide layer 134 modified or enhanced by the second capping layer 136. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 32 shows another semiconductor structure 19 b similar to the semiconductor structure 19, except for addition of the second capping layer 136. In greater detail, the second capping layer 136 is between the top electrode 108 and the second zirconium-containing oxide layer 134, and the second seed layer 132 is between the second zirconium-containing oxide layer 134 and the middle electrode 130. Combination of the second seed layer 132, the second zirconium-containing oxide layer 134 and the second capping layer 136 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the second zirconium-containing oxide layer 134 modified or enhanced by the layers 132 and 136. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 33 shows another semiconductor structure 19 c similar to the semiconductor structure 19, except for addition of the first capping layer 128 and omission of the first seed layer 120. The first capping layer 128 is between middle electrode 130 and the first zirconium-containing oxide layer 122. The first capping layer 128 can be a zirconium-free metal oxide layer that is capable of enhancing or modifying ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122. Suitable materials for the first capping layer 129 may be HfO₂, TiO₂ or combinations thereof. Combination of the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 34 shows another semiconductor structure 19 d similar to the semiconductor structure 19 a, except for addition of the first capping layer 128 and omission of the first seed layer 120. Combination of the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 35 shows another semiconductor structure 19 e similar to the semiconductor structure 19 b, except for addition of the first capping layer 128 and omission of the first seed layer 120. Combination of the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 36 shows another semiconductor structure 19 f similar to the semiconductor structure 19, except for addition of the first capping layer 128. Combination of the first seed layer 120, the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the layers 120 and 128 on opposite sides of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 37 shows another semiconductor structure 19 g similar to the semiconductor structure 19 a, except for addition of the first capping layer 128. Combination of the first seed layer 120, the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the layers 120 and 128 on opposite sides of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 38 shows another semiconductor structure 19 h similar to the semiconductor structure 19 b, except for addition of the first capping layer 128. Combination of the first seed layer 120, the first zirconium-containing oxide layer 122 and the first capping layer 128 provide negative capacitance due to the ferroelectricity or antiferroelectricity of the first zirconium-containing oxide layer 122 modified or enhanced by the layers 120 and 128 on opposite sides of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the second capping layer 136, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 39 shows another semiconductor structure 20 similar to the semiconductor structure 19, except for omitting the bottom electrode 104 and the middle electrode 130. In greater detail, the second seed layer 132 is in contact with the top surface of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 40 shows another semiconductor structure 20 a similar to the semiconductor structure 20, except for addition of the second capping layer 136 and omission of the second seed layer 132. In greater detail, the second zirconium-containing oxide layer 134 is in contact with a top surface of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 41 shows another semiconductor structure 20 b similar to the semiconductor structure 20, except for addition of the second capping layer 136. In some embodiments, the second capping layer 136 is between the top electrode 108 and the second zirconium-containing oxide layer 134. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 42 shows another semiconductor structure 20 c similar to the semiconductor structure 20, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the second seed layer 132 is in contact with the top surface of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 43 shows another semiconductor structure 20 d similar to the semiconductor structure 20 a, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the second zirconium-containing oxide layer 134 is in contact with the top surface of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 44 shows another semiconductor structure 20 e similar to the semiconductor structure 20 e, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the second seed layer 132 is in contact with the top surface of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 45 shows another semiconductor structure 20 f similar to the semiconductor structure 20, except for addition of the first capping layer 128. In some embodiments, the second seed layer 132 is in contact with the top surface of the first capping layer. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 46 shows another semiconductor structure 20 g similar to the semiconductor structure 20 a, except for addition of the first capping layer 128. In some embodiments, the second zirconium-containing oxide layer 134 is in contact with the top surface of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 47 shows another semiconductor structure 20 h similar to the semiconductor structure 20 b, except for addition of the first capping layer 128. In some embodiments, the second seed layer 132 is in contact with the top surface of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 48 shows another semiconductor structure 21 similar to the semiconductor structure 20, except for omitting the gate dielectric layer 118. In some embodiments, the first seed layer 120 is in contact with the channel region 126 of the substrate 102. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 49 shows another semiconductor structure 21 a similar to the semiconductor structure 21, except for addition of the second capping layer 136 and omission of the second seed layer 132. In some embodiments, the second zirconium-containing oxide layer 134 is in contact with the top surface of the first zirconium-containing oxide layer 122. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 50 shows another semiconductor structure 21 b similar to the semiconductor structure 21, except for addition of the second capping layer 136. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 51 shows another semiconductor structure 21 c similar to the semiconductor structure 21, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 52 shows another semiconductor structure 21 d similar to the semiconductor structure 21 a, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 53 shows another semiconductor structure 21 e similar to the semiconductor structure 21 b, except for addition of the first capping layer 128 and omission of the first seed layer 120. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

FIG. 54 shows another semiconductor structure 21 f similar to the semiconductor structure 21, except for addition of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132.

FIG. 55 shows another semiconductor structure 21 g similar to the semiconductor structure 21 a, except for addition of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second capping layer 136.

FIG. 56 shows another semiconductor structure 21 h similar to the semiconductor structure 21 b, except for addition of the first capping layer 128. In some embodiments, the first zirconium-containing oxide layer 122 has ferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has antiferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136. In some other embodiments, the first zirconium-containing oxide layer 122 has antiferroelectricity enhanced or modified by the first seed layer 120 and the first capping layer 128, and the second zirconium-containing oxide layer 134 has ferroelectricity enhanced or modified by the second seed layer 132 and the second capping layer 136.

Based on the above discussion, it can be seen that the present disclosure offers advantages. It is understood, however, that other embodiments may offer additional advantages, and not all advantages are necessarily disclosed herein. Moreover, no particular advantage is required for all embodiments. One advantage is that no annealing process is required to enhance or modify ferroelectricity or antiferroelectricity of the as-deposited ZrO₂ or Hf_(0.5)Zr_(0.5)O₂ layer and thus low thermal budget for deposition of layers of the semiconductor device is obtained, which is beneficial to process integration. Another advantage is that the thicknesses of the layers in the negative-capacitance gate stack can be reduced, resulting in further scaling down the NC-FET. Yet another advantage is that when the ferroelectric layer is made if ZrO₂, ferroelectricity or antiferroelectricity may be achieved in the ferroelectric layer without additional dopants. Still yet another advantage is that the ferroelectric layer can be prepared directly on the substrate without the gate dielectric layer. A further advantage is that when the ferroelectric layer is made of ZrO₂, by incorporating at least one of the seeding layer and the capping layer, either the ferroelectric phase or the antiferroelectric phase can be achieved, which provides flexibility in the formation of the NCFET. Another advantage is that ZrO₂ and Hf_(0.5)Zr_(0.5)O₂ are both compatible with silicon, and thus the ZrO₂ or Hf_(0.5)Zr_(0.5)O₂ layer can be directly deposited on the channel region of the silicon substrate without additional gate dielectrics.

In some embodiments, a device includes a substrate, a first zirconium-containing oxide layer, a first metal oxide layer and a top electrode. The first zirconium-containing oxide layer is over a substrate and having ferroelectricity or antiferroelectricity. The first metal oxide layer is in contact with the first zirconium-containing oxide layer. The first metal oxide layer has a thickness less than a thickness of the first zirconium-containing oxide layer. The top electrode is over the first zirconium-containing oxide layer.

In some embodiments, the device further includes a second metal oxide layer. The first zirconium-containing oxide layer is between the first metal oxide layer and the second metal oxide layer.

In some embodiments, the second metal oxide layer has a thickness less than the thickness of the first zirconium-containing oxide layer.

In some embodiments, the first metal oxide layer and the second metal oxide layer are made of the same material.

In some embodiments, the device further includes a second zirconium-containing oxide layer and a second metal oxide layer. The second zirconium-containing oxide layer is over the first zirconium-containing oxide layer. The second metal oxide layer is in contact with the second zirconium-containing oxide layer.

In some embodiments, the second metal oxide layer has a thickness less than a thickness of the second zirconium-containing oxide layer.

In some embodiments, the device further includes a third metal oxide layer. The second zirconium-containing oxide layer is between the second metal oxide layer and the third metal oxide layer.

In some embodiments, the third metal oxide layer has a thickness less than the thickness of the second zirconium-containing oxide layer.

In some embodiments, the second metal oxide layer and the third metal oxide layer are made of the same material.

In some embodiments, the first zirconium-containing oxide layer has ferroelectricity, and the second zirconium-containing oxide layer has antiferroelectricity.

In some embodiments, the first zirconium-containing oxide layer has antiferroelectricity, and the second zirconium-containing oxide layer has ferroelectricity.

In some embodiments, a device includes a semiconductor substrate, a first zirconium-containing oxide layer, a first metal oxide layer and a top electrode. The semiconductor substrate has source/drain regions and a channel region between the source/drain regions. The first zirconium-containing oxide layer is over the channel region of the semiconductor substrate and having ferroelectricity or antiferroelectricity. The first metal oxide layer is in contact with the first zirconium-containing oxide layer. The top electrode is over the first zirconium-containing oxide layer.

In some embodiments, the first metal oxide layer is over the first zirconium-containing oxide layer.

In some embodiments, the device further includes a second zirconium-containing oxide layer over the first zirconium-containing oxide layer and having ferroelectricity or antiferroelectricity.

In some embodiments, the second zirconium-containing oxide layer is between the first metal oxide layer and the top electrode.

In some embodiments, the device further includes a second metal oxide layer in contact with the second zirconium-containing oxide layer.

In some embodiments, the second metal oxide layer is between the first metal oxide layer and the second zirconium-containing oxide layer.

In some embodiments, the second metal oxide layer is between the top electrode and the second zirconium-containing oxide layer.

In some embodiments, a method includes forming source/drain regions in a semiconductor substrate; depositing a zirconium-containing oxide layer over a channel region in the semiconductor substrate and between the source/drain region; forming a metal oxide layer in contact with the zirconium-containing oxide layer; and forming a top electrode over the zirconium-containing oxide layer, wherein no annealing is performed after depositing the zirconium-containing oxide layer and prior to forming the top electrode.

In some embodiments, forming the metal oxide layer is performed such that the metal oxide layer is thinner than the zirconium-containing oxide layer.

The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the present disclosure. 

What is claimed is:
 1. A device, comprising: a substrate; a first zirconium-containing oxide layer over the substrate and having ferroelectricity or antiferroelectricity; a titanium oxide layer in directly contact with a top surface of the first zirconium-containing oxide layer, the titanium oxide layer has a thickness less than a thickness of the first zirconium-containing oxide layer; a top electrode over the titanium oxide layer; a first metal oxide layer between the titanium oxide layer and the top electrode; and a middle electrode between the titanium oxide layer and the first metal oxide layer.
 2. The device of claim 1, further comprising a second metal oxide layer between the first zirconium-containing oxide layer and the substrate.
 3. The device of claim 2, wherein the first metal oxide layer has a thickness less than the thickness of the titanium oxide layer.
 4. The device of claim 2, wherein the first metal oxide layer is made of titanium oxide.
 5. The device of claim 1, further comprising: a second zirconium-containing oxide layer over the first zirconium-containing oxide layer, wherein the first metal oxide layer is in contact with the second zirconium-containing oxide layer.
 6. The device of claim 5, wherein the first metal oxide layer has a thickness less than a thickness of the second zirconium-containing oxide layer.
 7. The device of claim 5, further comprising a second metal oxide layer, wherein the second zirconium-containing oxide layer is between the first metal oxide layer and the second metal oxide layer.
 8. The device of claim 7, wherein the second metal oxide layer has a thickness less than the thickness of the second zirconium-containing oxide layer.
 9. The device of claim 7, wherein the first metal oxide layer and the second metal oxide layer are made of the same material.
 10. The device of claim 5, wherein the first zirconium-containing oxide layer has ferroelectricity, and the second zirconium-containing oxide layer has antiferroelectricity.
 11. The device of claim 5, wherein the first zirconium-containing oxide layer has antiferroelectricity, and the second zirconium-containing oxide layer has ferroelectricity.
 12. A device, comprising: a semiconductor substrate having source/drain regions and a channel region between the source/drain regions; a first zirconium-containing oxide layer over the channel region of the semiconductor substrate and having ferroelectricity or antiferroelectricity; a first metal oxide layer in contact with the first zirconium-containing oxide layer, wherein the first metal oxide layer is electrically insulating; a top electrode over the first zirconium-containing oxide layer; a second zirconium-containing oxide layer between the first zirconium-containing oxide layer and the top electrode; a second metal oxide layer in contact with the second zirconium-containing oxide layer and made of a material different than the first metal oxide layer; and a middle electrode between the first zirconium-containing oxide layer and the second zirconium-containing oxide layer.
 13. The device of claim 12, wherein the first metal oxide layer is over the first zirconium-containing oxide layer.
 14. The device of claim 12, wherein the second zirconium-containing oxide layer has ferroelectricity or antiferroelectricity.
 15. The device of claim 14, wherein the second zirconium-containing oxide layer is between the first metal oxide layer and the top electrode.
 16. The device of claim 14, further comprising: a second metal oxide layer in contact with the second zirconium-containing oxide layer.
 17. The device of claim 16, wherein the second metal oxide layer is between the first metal oxide layer and the second zirconium-containing oxide layer.
 18. The device of claim 16, wherein the second metal oxide layer is between the top electrode and the second zirconium-containing oxide layer.
 19. A device, comprising: a substrate; a gate dielectric layer over the substrate; a bottom electrode over the gate dielectric layer; a titanium oxide layer over the bottom electrode; a zirconium-containing layer over the titanium oxide layer; a hafnium oxide layer over the zirconium-containing layer; a top electrode over the hafnium oxide layer; a zirconium-free metal oxide layer between the hafnium oxide layer and the top electrode; and a middle electrode in contact with a bottom surface of the upper zirconium-free metal oxide layer and a top surface of the hafnium oxide layer.
 20. The device of claim 19, wherein the bottom electrode includes Pt and the zirconium-containing layer includes zirconium dioxide, and the zirconium-containing layer has an antiferroelectric phase. 